Pressurized hair waving compositions



United States Patent U" 3 103,458 PRESSURIZED HAIR WAVING COMPOSITIONS William W. Shepard, Amelia, Mary Ellen Romney Baude,

Cincinnati, and Robert S. Moore, Wyoming, Ohio, as signors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Oct. 30, 1958, Ser. No. 770,604

7 Claims. (1. 167--87.1)

This invention relates to an improved method for the cold permanent Waving of hair and tocompositions, packaged in pressurized containers, for use in the improved method. t

The cold permanent waving of hair is accomplished by contacting the hair with some chemical composition which will soften and plasticize it at room temperature.

According to the present understanding in the art, such chemical compositions reduce the keratin structure of the hair, thereby breaking disulfide linkages. While the hair tresses are mechanically held in a new configuration, the disulfide linkages are restored by oxidation to fix the tresses in the new configuration.

In a conventional home waving procedure, the hair is first shampooed. After rinsing and removal of excess Water, thewindividual hair tresses are saturated with reducing lotion before being wound on a curler or mandrel. The individual hair tresses, after having been wound on the mandrel, are again saturated with reducing lotion. After a suitable period of time, the reducing lotion is removed from the hair with a .water rinse; and the reduced hair, while still wound on the mandrel, is fixed by application of :a chemical or by air oxidation. In the pin curl procedure, a few tr-esses saturated with lotion are formed on curlers as described, and the remainder are wound around a finger without prior saturation with lotion. The latter curls, held by bobby pins,

'are then, along with those on curlers, saturated with lotion. These curls are subsequently treated inthe same way as those held on curlers.

In the most commonly employed home waving procedures, the waving lotion is manually applied to the hair in the initial saturation step and again inthe resatu-..

ration step after the hair has been Wound on mandrels.

A cotton pad or sponge which is repeatedly saturated by.

being dipped into the lotion is used as an applicator. The disadvantages inherent in such a procedure are readily apparent. The independent saturation of each individual hair tress, performed before and after winding on the mandrel, is both tedious and time consuming. Most modern hair waving lotions have an alkalinity above pH 9 and may behave as irritants when repeatedly brought into direct contact with the skin of sensitive individuals. The commonly employed methods for applying waving lotion provide opportunity for prolonged and repeated contact of this alkaline solution with the hands as the subject satunates the applicator and then applies the applicator to the hair. Furthermore, if not carefully applied, the run-oil of lotion on the scalp and down the hands and wrists may be discomforting.

Recently attempts have been made to eliminate some of the opportunities for the lotion to contact the hands by applying the lotion directly from :a plastic squeeze bottle. A comb-tip may be used in the initial saturation step. This method does not eliminate the dripping of excess lotion from the tresses and requires the user to transfer the lotion solution from the glass package in which it is supplied to the plastic bottle. A further development has been to provide a catch tray which can be held under a Wound curl to catch the excess lotion as it runs off. The catch tray cannot be used in the -many products for household purposes.

ice

2 initial saturation and demands considerable manipulative skill from a woman who is waving her own hair.

The volatility IHIld susceptibility to oxidation of the active ingredients in many of the conventional hair waving lotions make the ordinary methods of commercial packaging inappropriate for a container of lotion which can be used and stored repeatedly without loss of activity. A type of packaging then, which will enable alternate use and storage should enjoy widespread consumer acceptance for touch-up waves as Well as for periodic full waving.

Pressurized containers or Iaerosol packages are well known and have been widely employed for packaging In spite of,its recognized advantages in other areas, this packaging technique has not previously been found to be acceptable for use in the field of cold permanent waving, not because of technical packaging difiiculties, but because of the inherentdemands of the cold waving technique. Even with the conventional hair waving procedures described hereinbe-fore, it is difficult to achieve the requisite uniform saturati on of the hair with lotion. The outside of a wound tress may receive a heavy concentration of the lotion, while the portion of the hair inside a wound curl may receive a much smaller amount. As a result, portions of the hair may be damaged by the too high concentration, and other parts of the hair may not be reduced at all because they are not contacted by sufiicient lotionto break the disulphide bonds. The usual aerosol methods which might be used to dispense hair waving lotion as a foam or mist are by their very nature lessable to meet the demands of cold hair Waving than is the conventional technique. On the one hand, a foam acts as a' physical impediment to the penetration of the reducing agent into the hair. On the other hand, a mist is unsatisfactory because of the wide diffusion of the hair waving lotion; most lotions are, to someindividuals,

unpleasant in odor and they may stain clothing. A liquid stream could be dispensed from a pressurized container but would be difficult to control so as to provide uniform saturation; this would be true even if the problem of lotion dripping from the hairlwere solved by having the stream form foam on impact with the hair.

The dispensing of products such as shaving cream and toothpaste as foams from pressurized containers is known in the art. In such products a stable foam is desired. The contents of the package are in the form of an emulsion or heterogeneous system and generally require gentle agitation before use. Examples of such lather producing compositions are disclosed by Spitzer et al. in US. Patent It is one of the objects of this invention to provide compositions packed in pressurized containers which make possible a novel andimproved method for waving hair.

It is another object to eliminate the manual "application of hair waving lotion to the hair, thereby reducing the possibility of skin irritation which may result from the contact of highly alkaline waving lotion with the hands.

It is a further object to provide a method for waving hair whereby run-off of excess lotion from the hair is prevented.

It is yet another object to provide a composition for waving hair suitable for packagingin such a manner that the product may be used for more than one wave and will not deteriorate between uses. i

Other objects and advantageous features will be apparent from the following detailed description. a

In brief, this invention comprises an improved hair waving procedure and compositions, packaged in pressurized contaiuers,'for use in the improved procedure.

hair tress. 1

-. are not skin sensitizers.

salts, can be added for their) pH stabilizing effect.

ingredients from the pressurized container.

stable foam which substantially completelybreaks or collapses to a liquid promptly after discharge. This tech- 'nique' inco'rpora'tes the ease of application of a foam and the requisite penetrabilit'y of a liquid and at the same time negates the limitations of both. The application ofthe lotion as an "unstable foam prevents run-off and yet permits the lotionto return fairly rapidly to a fluid-state which will be absorbed by the 'hairi-tress. The foam collapses at about the'rate at which the fluid penetrates the The compositions for use in the improved procedure must'have the characteristics which lead'to the fast break- Iing foam as well as those required for satisfactory cold waving of hair. .These hair waving compositions com- I prise a substantially single phase aqueous solution of a keratin-reducing agent, solvent for the propellant, and the dissolved or liquefied normally gaseous propellant.

Of course, part of the propellant and other volatile constituents will be in the vapor space.

Lowmoleoular weightwater-soluble mercaptans containing another functional group, 'such as carboxyl, hydroxyLor amide, in addition to the mercaptan-group are suitablekeratin-reducing agents for the waving lotions J. of this invention. The mercapto-alkanoic acids described .in U.S.' Patent 2,736,323 are preferred keratin-reducing substances because of their effectiveness and because they Among these, thioglycolic acid is especially preferred in the practice of this invention,

'and mercapto-propionic acid is almost equally suitable. -It is desirable to have the pH of the waving lotion above 7 to obtain'ra'pid and effective action and to have the pH below l'to a-void damaging the hair. A particularly desirable range is from pH 8.5 to pH 9.5. Any suitable alkali may be used to adjust the pH; but it is preferred to use a weak base as a major portion of the alkali, thereby providing desirable bulfering capacity. Suitable weak bases have dissociation contents of less than l0- and preferably less than "l0* they include ammonia, monoethanolamine, diethanolamine, tris(hydroxymethyl)- .rami'nome'thane and 2-amino-2-methy1l,3-propanediol.

Triethanolamine'and gl-ycerylamine are further examfples of bases which may be used. Monoethanolamine is an especiallypreferred Weak base. When the pH of the lotion is adjusted'to the preferred range with a weak base, there will usually be present free base in exces of that required'to form the salt of the mercapto-alkanoic acid. Examples of strong bases which may be used in minor proportions in conjunction with weak bases in this invention are sodium hydroxide, lithium hydroxide, Potassium hydroxide, and strong organic bases such as tetramethylammonium hydroxide. Mixtures of weak bases can be employed, and' it is often advantageous to do so. Soluble carbonates and bicarbonates, such as ammonium Use of a thioglycolate salt in preparing the lotion is, of course, equivalent to preparing itin' situ from thioglycolic acid and the appropriate base. 7 I

The keratin-reducing "agent is incorporated into the lotion at a'level equivalent to from'l to about weight percent, based on the total composition, of thioglycolic acid; The preferred compositions contain keratin-reducing agent at a level equivalent to from about 3 to about 6% thioglycolic aid. 7

A propellant isrequired to force the solution of active While any liquefiable gas having the proper vapor pressure can be considered, ,fluorinated and chlorinated hydrocarbons have found widespread use as propellants in aerosol packfluoromethane, dichlorotetrafluoroethane, difluoroethane,

involves a novel step which trichlorotri-fluoroethane and monochlorodifluoroethane. The choice of the best propellant for a particular formulation from among these and similar compounds is made on the basis of a low rate of hydrolysis of the carbon-chlorine bond in the aqueous solutions of this invention, an appropriate vapor pressure at a convenient level of propellant, and, most critically sufficient solubility in the aqueous solutions of the compositions of this invention. Particularly useful compounds from those named above are diof from 1% to 10% by weight of the total composition.

However, the quantity of propellant used depends upon the identity of the propellant, the'pressure desired in the container, the solubility of the propellant in the particular composition, and other factors. Mixtures of dichlorodifiuoromethane and dichlorotetrafluoroethane are usually employed at from about 3% to about 7% of the total composition if surface active agents are present; if surfaceactive agents are not present the propellant mixture is usually employed at from about 6% to about 10% of the totahcomposition. As the ratio of dichlorodifluoromethane to dichlorotetrafluoroethane in the propellant mixture is' increased, it is'preferable to decrease the quantity of the propellant mixture used. The lower limit of propellant content is'set by the emergence of the product as a weak and'runtny foam rather than the stiff, dry foam'which' is desired. If too large quantities of propellant are used, the pressure may exceed the safe limits for the typeof container being used, or the foam may be discharged in spurts rather than at a steady rate as is desired.

While it is not absolutely necessary to include a surface active agent in the compositions of this invention, it is generally 'dwirahle to do so. Where the composition of "the product'is such that the propellant is highly soluble, "as when from about 40% to about ethanol is used,

and when relatively large quantities of propellant, in the range of from about 6% to about 10% of the total composition, are used, a'satisfactory'foam can be obtained without a surface active agent. However, in the preferred 'practiceof this invention a surface active agent is'used thus enabling the achievement of a stiff, dry fast breakingjfoam with a smaller quantity of propellant. Fast breaking is intended to means a foam which breaks in less than 30 seconds after discharge onto the hair and preferably in lless than about 'l0l5 seconds. If too much surface active agent is employed the foam'tends to become very denseand to break too slowly; enough must be used to achieve the desired type of foam. Suitable surface active agents are found among the anionic detergents and among nonionio'de'tergents. Anionic detergents are preferred for the compositions containing alcohol and the 'mixed diohlor'otetnafiuoroethanedichlorodiiluoromethane propellants. Anionic or n onionic detergents can be em 'ployed for the other compositions. The "anionic detergent may be of the synthetic type or it may be a soap of a fatty acid. In either event, it is perferred that the cation of the detergent be one which confers high solubility on'the detergent; with this limitation, the cations of the alkalizing agents Llisted hereinbefore may be used. The choice of a surface active agent is not critical, most of those commonly employed in shampoos and other personal products being satisfactory.

Examples of anionic synthetic detergents suitable for the practice of this invention are the detergents of the sulfonated and sulfated types such as the alkyl (C3-'C13) sulfates, the alkyl (Cg-C1 polyethenoxy (1-10 units of C H O) ether sulfates, the alkyl (C -C aromatic sulfona-tes, the monoor di-alkyl (C -C esters of sulfosuccinic acid, sulfonated or sulfated amides of higher fatty acids, sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, higher fatty acid esters of low molecular weight alkytlol sulfonic acids, etc, usually in the form of their sodium, potassium, ammonium, or allcanol-ammonium salts. Some of th particular detergents of this category are: sodium octyl sulfate, sodium nonyl sulfate, sodium decyl sulfate, monoethanolammonium dodecyl sulfate, ammonium tetradecyl sulfate, monoethanolammonium pentadecyl sulfate, monoethanolammonium hexadecyl sulfate, monoethanolammonium octadecyl sulfate, monoethanolarnmonium oleyl sulfate, sodium salts of dioctyl sulfosuccinate, sodium octyl benzene sulfonate, sodium nonyl benzene sulzfonate, sodium dodecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, ammonium pentadecyl benzene sulfionate, ammonium triisopropyl benzene lsulfonate, dium salts of the oleic acid ester of isethionic acid, sodium salt of the lauric acid. amide of taurine, triethanolammonium coconut oil monoglyceride monosulfate, monoethanolammonium taillow diglyceride monosulfate.

Mixtures of various of the anionic synthetic detergents also come within the scope of the general class definition above. For example, the commercially available detergents are generally not pure compounds but are mixtures of homologous compounds. Thus, sodium alkyl benzene sulfonate wherein the alkyl group contains 12 to 18 carbon atoms, a mixture of triethanolammonium \alkyl sulfates consisting mostly of triethanolammonium llauryl sulfate, and a mixture of monoethanolammonium polyethenoxy ether sulfates wherein the alkyl group contains from 1 2. to 18 carbon atoms and there are from 1 to 6 units of -C H O per molecule, are well-known detergents. Mixtures of soaps andanionic synthetic detergents can be employed. As a further example of commercially important mixtures, alkanolammonium salts of coconut sulfate and coconut polyethenoxy ether sulfate are \among the detergents which are highly suitable for use in this invention. The coconut alkyl radical is derived from the middle distillation cut and typically will contain the following percentages of various chain lengths: C -2%, C '6 6%, C 23% and C 9%.

Examples of fatty acid soaps which are suitable for the practice of this invention include the soluble sodium, potassium, ammonium, and alkanolammonium salts of saturated and unsaturated fatty acids with from 10 to 18 carbon atoms and mixtures thereof. Specific examples of such soaps are monoethanolammonium laurate, myristate, palmitate, steauate and oleate. The use of commercially available mixtures will often be preferred, the soluble soaps of the middle distillation cut of coconut fatty acids, and consisting predominantly of C and C fatty acids, being especially suitable. When the surface active agent employed is a fatty acid soap it is generally desirable to include in the composition a highly effective calcium sequestering agent such as, an aminopolycarboxylate salt. This prevents the deposit of hard water soap on the hair when rinsing the lotion from the hair with ordinary tap Water. Particularly suitable are the soluble sodium, potassium, ammonium and alkanolammonium salts of ethylenediaminetetraacetic acid.

Water-soluble nonionic synthetic organic detergents are suitable for use in this invention; they include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic cornpoundwbich may be aliphatic or alkyl aromatic in na- Iture. Examples of such detergent would be: the polyalkylene glycol esters, ethers, and thioethers of the types,

wherein R represents long chain allkyl radicals having from about 8 to about 18 carbon atoms and n is an integer from about 4 to about 30; the polyethylene oxide condensates of alkyl phenols, etg. the condensation products of alkyl phenols having about 6 to 12 carbon atoms in the alkyl group, in either straight chain or branched chain configuration, with ethylene oxide in amounts equal to 1 0 to 25 moles of ethylene oxide per mole of alkyl phenol; compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol; the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. Compounds with ether linkages are preferred because of their resistance to hydrolysis in alkaline solutions. More specific examples of some suitable non-ionic detergents are: the reaction products of t-octylphenol with an average of from 9 to 30 moles of ethylene oxide per mole, and the water-soluble waxy reaction products of Ilauryl alcohol and ethyleneoxide having a titer of about 35 C. or higher and of oleyl alcohol and ethylene-oxide having a titer of about 29 C. or higher.

The quantity of surface active agent, when it is employed, is from 0.0% to 10%. However, the exact amount to be employed is determined by the remaining ingredients of the product as they affect the attainment of the fast breaking foam. With a mixture of dichlorodifluoromethane and dichlorotetralluoroethane as propellant and alcohol present, an anionic synthetic detergent or IE. fatty acid soap is preferred; from about 2% to about 9% will be used. The surface active agents serve the purposes of solubilizing or emulsifying the perfume, contributing to the solubilization of the propellant, and contributing to the production of a foam having the desired characteristics.

The solvent in the compositions of this invention is water, but it is desirable to add another solvent to increase the solubility of the propellant. With dichlorotetrafluoroethane and dichlorodifluoromethane as propellants, from 30% to 60%, by weight, of ethanol, based on the total composition, is preferably included. The lower limit is set by attaining the minimum content of dissolved propellant; and the upper limit is set by the increased flammability and irritating properties of the composition. When ethanol is used in the absence of surface active agent, it is generally preferred to employ from about 40% to about 60% by weight of the total composition. Surface active agents tend to increase the solubility of the propellants as does the ethanol. In a composition employing both surface active agent and ethanol, the latter should preferably be present in amount from about 30% to about 50% of the total composition. Other low molecular weight hydroxy compounds, including propyl and isopropyl alcohol can be employed in this invention.

Various minor ingredients can be included in the compositions of this inyention and are generally desirable for the purposes of making the product more pleasant to use and leaving the hair in a particularly good conditwo. It is generally desirable to include a soluble salt of the disulfide of the keratin-reducing agent, especially the disulfide of thioglycolic acid, at a level, based on the total composition, equivalent to from about 0.5% to 5% of dithiodiglycolic acid. The soluble salts which can be used include those formed from :the bases listed as suit able for making the pH adjustment. These additives protect the hair from over-treatment and leaye it in a particularly good condition as is disclosed in US. Patents 2,719,814 and 2,719,815. In the preferred compositions of this invention, a perfume will be added.

The compositions of this invention must be packaged in suitable pressure-tight containers. For pressures lower than about 25 p.s.i.g. at 70 F., glass bottles, which are coated on the outside with plastic, and metal cans are suitable. Metal cans are employed for higher pressures. A metal which is not appreciably corroded by the product should be chosen or a corrosion inhibitor, as is known in the art, should be added to the formulation. The valves, with which the pressurized containers are fitted to control their opening and discharge of product, are those commercially employed for other aerosol products. Nozzles for discharge of the product are not critical except that it is preferred to use a foam type nozzle. This type of nozzle provides opportunity for an appreciable pressure drop while the product is still confined within the nozzle. This pressure drop within the enclosed channel causes toam to be generated within the nozzle. Foam nozzles are commercially available and have been repeatedly described in the literature. For example, the U.S. Patent 2,655,480 of Spitzer et al. shows a typical foam nozzle. For additional convenience a comb-type applicator which discharges the foam from its teeth over the width of the tress can be used on the nozzle.

in the following, specific examples are set forth as illustrative of the invention and ofcertain of the relationships important in its practice. Compositions are expressedin weight percent. An entry such as Thioglycolic acid (as monoethanol ammonium salt) 5% means that the composition contains rnonoethanolammonium thioglycolate equivalent to 5% thioglycolic acid.

Example I The following composition was. prepared and intro duced into pressurized aluminum cans and plastic covered glass bottles fitted with valves to control the discharge of the product and with foam nozzles.

Percent Thioglycolic acid (as monoethanolammonium salt) 5.0

Dithiodiglyco'lic acid (as monoethanolammonium salt) 2.0 Monocthanolammonium coconut soap 3.9 Thiethanolammonium coconut sulfate 2.0 Sodium ethylenediaminetetraacetate 3.9 Perfume 0.5 Ethanol 40.0 Dichlorotetrafiuoroethane (Genetron 32.0) 5.9 Dich-lorodifluoromethane (Genetron 12) 1.1 Monoethanolamine to adjust the pH to 9.3 ca 2.2 Water Balance 1 The soap of coconut fatty acids which are predominantly CuH aCOOH and CmHmCOOH.

The coconut alkyl radical consisting predominantly of The composition of Example I, except that the quantity of propellant was reduced to 5.9% dichlorotetrafluoro ethane and 0.90% dichlorodifluoromethane, was introduced into a plastic covered pressurized container fitted with a valve and a foam nozzle.

This composition was highly suitable for use in the cold waving of hair according to the following pin-curl procedure. The hair was shampooed and rinsed. Certain tresses were saturated, one-by-one, by discharging the composition of this example from thepressurized container as a quickly breaking, stiff dry foam; and the tresse-s were formed into the desired configuration by the subject using customary curlers. Other tresses were, one-by-one, wound about a finger and fiastened in the curled configuration with bobby pins. The wave lotion was then discharged from its container onto the individual curls in the form of a stiff dry foam which collapsed within 10 to 15 seconds of the moment of release. Thirty minutes after application, the hair was thoroughly rinsed with warm water and allowed to dry for six hours. An excellent wave was obtained in the combed-out hair which was in good condition.

Example III The following composition was prepared and packed in a pressurized can fitted with a valve and a foam nozzle.

This composition exerted a vapor pressure of 27 p.s.i.g. at 70 It was unnecessary to include a surface active agent in this composition because of the high concentration of alcohol which solubilized the perfume and. the high level of propellant.

It was applied as a foam to hair wound in curls, as in Example H, on one half of a subjects head. The foam broke within about 15 seconds of its, discharge from the container. Lotion was applied in the conventional way to the curls on the other half of the head. After rinsing, drying for six hours, and combing, resulting waves were about equal in tightness of curls. They remained about equal in permanency of curls. Application of a foam from a pressurized can proved to be neater and quicker, the need for dipping the applicator in the lotion being eliminated, than application of a liquid from a sponge.

Example IV Two basic formulas were prepared as follows:

The quantity of propellant consisting of dichlorotetrafluoroethane (Genetron 320) and 15% dichlorodifluoromethane (Genetron 12) was varied in compositions A and B; the pressure inside the can and the quality of the discharged foam were observed. The data obtained, which are approximate, are:

In composition A, from 3.8% to 4.3% propellant (corresponding to 14.5 to 18.5 p.s.irg. pressure) gave a weak and runny foam; from 4.3% to 5.7% (18.5 to 23 p.s.i.g.) gave a good foam delivered at a steady rate; above 23 p.s.i.g., the foam spur-ted from the nozzle. In composition B from 3.9% to 6.2% propellant (corresponding to 7.4 to 15 p.s.i.g. pressure) gave a weak and runny foam; from 6.2% to 8.9% '(15 to 2d p.s.i.g.) gave a good foam delivered at a steady rate; above 21 p.s.i.g. the foam spurted from the nozzle. The solubility of propellant in composition A was about 5.5% and in composition B was about 11.2%.

Composition A and composition B containing 6.0% and 8.0% of propellant, respectively, were each tested by more than 100 women using the pin curl procedure of Example II. The acceptance of the new method of applying a fast breaking foam from a pressurized container directly to the hair was good.

Example V Aluminum pressure-tight cans provided with. a discharge valve and foam nozzle were used to contain the following composition which was substantially a homogeneous solution.

Percent Thiog-lycolic acid (as monoethanolammonium salt) 5.0 Dithiodiglycolic acid (as monoethanolammonium 1 As defined in Example I.

The composition discharged through a 'valve from a foam nozzle as a stifi, unstable, quickly breaking foam. The pressure in the container was about 40 p.s.i.g. at 70 F. It was successfully used to cold Wave hair.

The objects of this invention will also be achieved if dithiodiglycolic acid is omitted [from the above formulations or if thioglycolic acid is replaced by mercaptopropionic acid and the dithiodiglycolic acid is omitted. Instead of monoethanolammonium salts, the salts of diethanolamine, Z-amino-Z-methyl-1,3-propanediol, or tris- (hydroxymethyl)amminomethane can be employed.

The term consisting essentially of as used in the definition of the ingredients present in the composition claimed is intended to exclude the presence of other materials in such amounts as to interfere substantially with the properties and characteristics possessed by the composition set forth but to permit the presence of other materials in such amounts as not substantially to affect said properties and characteristics adversely.

What is claimed is:

1. A pressurized permanent cold hair waving composition adapted for discharge from its container as a foam which collapses to a liquid within 30 seconds after discharge, consisting essentially of about 1% to about 10% of a low molecular weight mercapto-alkanoic acid, an alkalizing agent a substantial part of which is a base with a dissociation constant less than 10' imparting to the composition a pH above 7 but below :10, from about 1% to about 10% of a propellant selected from the group consisting of monochlorodifluoromethane, dichlorodifluoromethane, trichloromonofluoromethane, dichlorotetrafluoroethane, difluoroethane, trichlorotrifluoroethane, monochlorodifluoroethane, and mixtures thereof, from about 0.05% to about 10% of a surface active agent, and a solvent which is an aqueous-lower molecular weight alcohol solution wherein the amount of alcohol is from about 30% to about 60% of the total composition and which is sufficient to dissolve substantially completely all non gaseous components of the composition into a substantially homogeneous single liquid phase.

2. The composition of claim 1, substantially free of surface active agents, in which the solvent is aqueous ethanol, the ethanol being from about 40% to about 60% of the total composition; and in which the propellant is a mixture of dichlorotetrafluoroethane with dichlorodi- .fiuoromethane, the propellant being from about 6% to discharge from its container as a foam which collapses to a liquid Within 30 seconds after discharge, substantially free of surface active agent and consisting essentially of from 1% to 10% thioglycolic acid; an alkalizing agent, a substantial part of which is a base with a dissociation constant less than 10* to adjust the pH to from 8.5 to 9.5; a solvent which is aqueous ethanol, the ethanol being from about 40% to about 60% of the total composition; from about 6% to about 10% of a propellant which is a mixture of from about to about 40% of dichlorotetrafluoroethane with dichlorodifluoromethane, the non-gaseous portion of said composition being a substantially homogeneous solution.

5. A pressurized hair waving composition adapted for discharge from its container as a foam which collapses to a liquid within 30 seconds after discharge, consisting essentially of from 1% to 10% thioglycolic acid; an alkalizing agent, a substantial part of which is a base with a dissociation constant less than 10' to adjust the pH to from 8.5 to 9.5; a solvent which is an aqueous ethanol solution of an anionic surface active .agent, the ethanol being from about 30% to about 50% of the total composition, and the surface active agent being from about 2% to about 9% of the total composition; and from about 3% to about 7% of .a propellant which is a mixture of from about 95% to about 40% of dichlorotetrafluoroethane with dichlorodifiuoromethane, the non-gaseous portion of said composition being a substantially homogeneous solution.

6. A package comprising a pressure-tight container having a valve-controlled opening to a foam nozzle and containing a hair waving composition substantially free of surface active agents and adapted for being discharged as an unstable foam which collapses to a liquid within 30 seconds after discharge, consisting essentially of: from about 3% to about 6% thioglycolic acid; an agent to adjust the pH from about 8.5 to about 9.5 selected from the group consisting of monoethanolamine, diethanolamine, ammonia, 2-amino-2-methyl-1,3-propanediol, tris (hydroxymethyl)aminomethane and mixtures thereof;

from about 40% to about 60% ethanol; from about 6% to about 10% of .a mixture of from about 95% to about 40% of dichlorotetrafluoroethane with dichlorodifluoromethane; and water, the non-gaseous portion of said composition being a substantially homogeneous solution.

7. A package comprising a pressure-tight container having a valve-controlled opening to a foam nozzle and containing a hair waving composition adapted for being discharged as an unstable foam which collapses to a liquid Within 30 seconds after dicharge consisting essentially of: from about 3% to about 6% thioglycolic acid; an agent to adjust the pH from about 8.5 to about 9.5 selected from the group consisting essentially of monoethanolamine, diethanolamine, ammonia, 2-amino-2-methyl-1,3- propanediol and tris(hydroxymethyl)aminomethane and mixtures thereof; from about 2% to about 9 of a soluble anionic detergent selected from the group consisting of synthetic anionic detergents and fatty acid soaps and mixtures thereof; from about 30% to about 50% ethanol; from about 3% to about 7% of a mixture of from about 95% to about 40% of dichlorotetrafluoroethane with dichlorodifluoromethane; and water, the non-gaseous por- 'tion of said composition being a substantially homoge- Downing et-a1.: S0ap-and Sanitary-Chemicals,Septem- 1160118. Solution. ber 1953, pp. 142, 143, 145,147, 149,153, 155, 177-179. \Refe 'ences =ited in th'efile of thislpatent e fi fi lisi z fsgfi speclal'nes H I v UNITED STATES PATENTS '5 Herzka: J .YSocJCosmetic Chemists, July 1956, pp. 346- 2,655,480 "Spitzer'et a1 Oct. 13, 1953 364, 29 7 3 Allen et 1959 Sagarin: Cosmetics, Science and Technology, iInter- 3992555 June/4, 1963 science Publ., NY. 1957 pp. 8224325.

OTHER REFERENCES "1'0 -De Navarre, Am. Per'f. an'd'Ess. Oil Review, May 1956,

Sa'ga'rin: Cosmetics, Science and Technology, Intersci. "l

Publ.,"N."Y. '(1957),"pp. 610- 611 and 836. 

1. A PRESSURIZED PERMANEMT COLD HAIR WAVING COMPOSITION ADAPTED FOR DISCHARGE FROM ITS CONTAINER AS A FOAM WHICH COLLAPSES TO A LIQUID WITHIN 30 SECONDS AFTER DISCHARGE, CONSISTING ESSENTIALLY OF ABOUT 1% TO ABOUT 10% PF A LOW MOLECULAR WEIGHT MERCAPTO-ALKANOIC ACID, AN ALKALIZING AGENT A SUBSTINAL PART OF WHICH IS A BASE WITH A DISSOCIATION CONSTANT LESS THAN 10-5 IMPARTING TO THE COMPOSITION A PH ABOVE 7 BUT BELOW 10, FROM ABOUT 1% TO ABOUT 10% OF A PROPELLANT SELECTED FROM THE GROUP CONSISTING OF MONOCHLORODIFLUOROMETHANE, DICHLORODIFLUOROMETHANE, TRICHLOROMONOFLUOROMETHANE, DICHLOROTETRAFLUOROETHANE, DIFLUOROETHANE, TRICHLOROTRIFLUROETHANE, MONOCHLORODIFLUOROETHANE, AND MIXTURES THEREOF, FROM ABOUT 0.05% TO ABOUT 10% OF A SURFACE ACTIVE AGENT, AND A SOLVENT WHICH IS AN AQUEOUS-LOWER MOLECULAR WEIGHT ALCOHOL SOLUTION WHEREIN THE AMOUNT OF ALCOHOL IS FROM ABOUT 30% TO ABOUT 60% OF THE TOTAL COMPOSITION AND WHICH IS SUFFICIENT TO DISSOLVE SUBSTANTIALLY COMPLETELY ALL NON-GASEOUS COMPONENTS OF THE COMPOSITION INTO A SUBSTANTIALLY HOMOGENEOUS SINGLE LIQUID PHASE. 